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US3310510A - Polyolefins stabilized with the combination of a nickel salt of a carboxylic acid and a phenolic antioxidant - Google Patents

Polyolefins stabilized with the combination of a nickel salt of a carboxylic acid and a phenolic antioxidant Download PDF

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US3310510A
US3310510A US386441A US38644164A US3310510A US 3310510 A US3310510 A US 3310510A US 386441 A US386441 A US 386441A US 38644164 A US38644164 A US 38644164A US 3310510 A US3310510 A US 3310510A
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bis
alkylphenol
nickel
phenol
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David S Breslow
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

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  • the present invention relates to polyolefin compositions and, more particularly, to the stabilization of polyethylene and stereoregular polymers of propylene and higher ot-olefins against degradation by light.
  • the combination of a nickel salt of a hydrocarbon carboxylic acid and a small amount of a phenolic antioxidant is highly effective in stabilizing polyethylene and the stereoregular polymers of propylene and higher a-olefins against degradation by light.
  • the invention relates to polyethylene and stereoregular polymers of and-olefin having at least 3 carbon atoms containing as light stabilizer therefor a small amount of a nickel salt of a hydrocarbon carboxylic acid containing 2 to 22 carbon atoms and a phenolic antioxidant.
  • hydrocarbon carboxylic acid is meant any carboxylic acid derived from a hydrocarbon by substituting a COOH group for a hydrogen atom.
  • any polymer of a Il'lOIlO-u-Olfififl having at least 2 carbon atoms can be stabilized by means of the invention
  • the invention is particularly useful is stabilizing stereoregular polymers of monoolefins having from 3 to 6 carbon atoms, including, for instance, polypropylene, poly (butene 1), poly(pentene 1), poly(3 methylbutene-l), and poly(4 methylpentene 1).
  • Polyethylene even though it degrades under the influence of light by a mechanism somewhat different than the above stereoregular polymers, is also susceptible to stabilization by the invention.
  • the nickel salts of the hydrocarbon carboxylic acids that are used to produce the compositions of the invention are known to the art and include, by way of example, the nickel salts of isobutyric, isovaleric, caproic, 2-ethylbutyric, 2-methyl-pentanoic, n-octanoic, 2-ethylhexanoic, 2,2,4,4-tetramethylpentanoic, 2,4,6-trimethylheptanoic, 5,7-dimethyloctanoic, pelargonic, lauric, tridecanoic, myristic, palmitic, stearic, naphthenic, 3-methylcyclohexane, carboxylic, 4-isopropylcyclohexane carboxylic, cyclohexane acetic, bicyclo(2,2,1) carboxylic, p(1,1,
  • the phenolic antioxidants used to produce the compositions of the invention are also well known.
  • Such antioxidants include, for example, polysubstituted phenols, poly(alkylphenol) substituted hydrocarbons, hydroxyphenyl polyalkylchromans, adducts of an alkylphenol and a cyclic terpene, thiobis(alkylphenol)s, and hydroxyphenoXy substituted triazines.
  • the A-stage para-tertiary alkylphenol-formaldehyde resins such as are described in US. 2,968,641 are also suitable.
  • the polysubstituted phenols that can be used are either dior trisubstituted phenols. Particularly preferred are the 2,4,6-trialkylphenols described in US 2,581,907 to Smith, Jr., et al., the 2-aralkyl-4,6-dialkyl substituted phenols described in US. 2,967,853 to Spacht, and the mono-, di-, and tri(dialkyl hydroxybenzyl) phenols described in US. 3,053,803 to latte, Rocklin, and Van Winkle.
  • Inclusive of the trialkylphenols are: 2,4-dimethyl 6 tert-butylphenol, 2,4-dirnethyl-6-(alpha,alpha,gamma,gamma tetramethylbutyl) phenol, 2,6-di-tert-butyl-4- methylphenol, 2-methyl-4,6 di tert-butylphenol, 2,6-ditert-butyl-4-sec-butylphenol, 2,4,6-tri-tert-butylphenol, 2, 4,6-triethylphenol, 2,4,6-tri-n-propylphenol, 2,4,6-triisopropylphenol, 2,6-di-tert-octyl-4-propylphenol, 2,6-di-tertbutyl-4-ethylphenol, 2,4-dicyclohexyl-6-methylphenyl,- 2- isopropyl 4 methyl 6-tert-butylphenol, 2,4-dimethyl- 6- tert-
  • the preferred compounds of this class are those which"have primary or secondary aralkyl groups or secondary or tertiary alkyl groups at the 2- and 6-position and a normal alkyl group at the 4-position, a representative of this class More preferably, the normal alkyl group in the 4-position is one containing from about 1 to 20 carbon atoms while the secondary or tertiary alkyl groups in the 2- and 6-positions each contain from about 3 to 20 carbon atoms.
  • the preferred aralkyl dialkyl substituted phenols are those which have a primary aralkyl radical, a secondary aralkyl radical, or a tertiary alkyl radical having 4 to 12 carbons ortho to a hydroxyl group. Particularly suitable are 2-alphaphenylethyl-4-methyl-6-tert-butylphenol and 2- alphaphenylethyl-4-methyl-6-tert-octylphenol.
  • Particularly preferred mono-, di-, and tri(dialkyl hydroxylbenzyl) phenols include: p-(3,5-di-tert-butyl-4-hydroxybenzyl) phenol, p-(3,Sadiisopropyl-4-hydroxybenzyl)phenol, o-(3- methyl-S-isopropyl-4-hydroxybenzyl)phenol, o (3-butyl- 5-tert-amyl-4-hydroxybenzyl)phenol, o-(3-5-di-tert-arnyl 4 hydroxybenzyl)phenol, 2,6 di(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, 2,6 di(3,5 di tert butyl 4 hydroxybenzyl)-4-methylphenol 2,6 di(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,6 di(3-rnethyl-5- tert-amyl-4-hydroxybenzyl)phenol
  • the alkylidene-bis(alkylphenol)s are characterized by the general formula wherein R is an alkylidene radical of l to 5 carbon atoms and wherein R is an alkyl group of 1 to 12 carbon atoms and n is an integer from 1 to 3 and m is an integer from 1 to 2.
  • R is an alkylidene radical of l to 5 carbon atoms and wherein R is an alkyl group of 1 to 12 carbon atoms and n is an integer from 1 to 3 and m is an integer from 1 to 2.
  • each R can be the same or dilferent.
  • alkylidene-bis(alkylphenol)s that may be used are 2,2'-methylene-bis 5--isopropylphenol 2,2'-methylene-bis (4-methyl-6-isopropylphenol 2,2'-methylene-bis(4-methy1-6-tert-butylpheno1) 2,2'-methylene-bis 4-tert-butyl-6-methylphenol 2,2' methylene-bis-(4,6-di-tert-butylphenol 2,2-methylene-bis 4-nonylphenol 2,2'-methylene-bis [4methyl-6-( l-methylcyclohexyl) phenol] 2,2'-methylene-bis (4-decyl-phenol) 4,4'-methylene-bis( 5-methyl-2-tert-butylphenol 4,4'-methylene-bis 5-methyl-2-( l-methylcyclohexyl) phenol] 4,4'-methylene-bis 2,6-di-tert-butylphenol 2,2'-is
  • cycloalkylidene bis(alkylphenol)s are also suitable.
  • benzylidene-bis (alkylphenol)s are also suitable.
  • his or tris dialkyl hydroxybenzyl)alkyl benzenes.
  • hydroxyphenyl polyalkylchromans are the 2- (or 4) (*2-hydroxyphenylchromans which have one of the following general formulae:
  • each R may be hydrogen or alkyl, but at least one R in each of the aromatic rings is alkyl.
  • These compounds may also be named as benzopyrans.
  • the 2(2-hydroxyphenyl)chromans may be named as 2,3-dihydro-2(2'-hydroxyphenyl)-1,4-benzopyrans or 3,4-dihydro-2(2-hydroxyphenyl)-1,2-benzopyrans and the 4(2'- hydroxyphenyl)chromans may be named as 2,3-di-hydro- 4(2-hydroxyphenyl) 1,4 benzopyrans or 3,4-dihydro- 4(2'-hydroxyphenyl)-1,2-benzopyrans.
  • the 2(2'-hydroxyphenyl)chromans are also sometimes named as flavans, i.e., 2'-hydroxy-flavans.
  • the alkyl substituents in each of the aromatic rings may be any alkyl radical, as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertbutyl, amyl, hexyl, isohexyl, octyl, isooctyl, 'Z-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, etc.
  • At least one alkyl radical in each aromatic ring will contain at least four carbon atoms or the sum of the carbon atoms in the alkyl radicals in each ring will be at least four.
  • Exemplary of these 2- (or 4) (2-hydroxyphenyl)chromans are 2 2-hydroxyphenyl -2,4,4,5 ',6-pentamethylchroman,
  • the terpene-phenol adducts that are used in accordance with the invention are known materials that have been Generically defined, they are adducts of phenol or an alkylphenol that contains from 1 to 2 alkyl substituents of 1 to 10 carbon atoms each and a cyclic unsaturatedterpene or dihydroterpene of empirical formula C H or C H respectively. They'can be prepared by condensing phenol, or an alkylphenol, with the terpene, or dihydroterpene, in varying ratios in the presence of an acidic catalyst.
  • Suitable cyclic terpenes and dihydroterpenes from which the aforesaid adducts can be made include carvomenthene, dipentene, a-pinene, a-terpinene, terpinolene, Z-menthene, 3-menthene, dihydroterpinolene, dihydrodipentene, camphene, A -carene, p-pinene, and the like.
  • Suitable phenols in addition to phenol itself, include the various isomeric cresols, 2,4-xylenol and other isomeric xylenols, p-sec-butylphenol, p-isopropylphenol, o-isopropylphenol, m isopropylphenol, 0,0 diisopropylphenol, o,o'-di-tert-butylphenol, o amylphenol, o nonylphenol, and similar compounds.
  • the two reactants can be condensed in varying ratios. Any ratio within the range of 0.3 to 3 moles of terpene or dihydroterpene per mole of the phenolic compound is satisfactory, but it is preferred to employ a ratio within the narrower range of 0.5 to 2.5 moles of terpene or dihydroterpene per mole of the phenolic compound.
  • the adduct formation is carried out by contacting the two reactants in the presence of an acid catalyst at a temperature within the range of about to 150 C. and allowingthe reaction to proceed.
  • An inert solvent may be used as a reaction medium for convenience, if so desired. Normally, the reaction will go to substantial completion in from 1 /2 to 5 /2 hours. Upon termination of the reaction, unconsumed reactants and volatile byproducts can be removed by distillation at reduced pres sure since the adducts themselves are high boiling materials.
  • the acid catalyst can be any of those acids or acidic compounds that are useful catalysts in condensation reactions generally. These include mineral acids such as sulfuric acid, organic acids such as p-toluene sulfonic acid, boron trifluoride and its derivatives, as, for instance, complexes of boron trifluoride and an ether, e.g., boron trifluoride-ethyl ether complex, metal chlorides such as aluminum chloride and stannic chloride, and acidic clays.
  • mineral acids such as sulfuric acid
  • organic acids such as p-toluene sulfonic acid
  • boron trifluoride and its derivatives as, for instance, complexes of boron trifluoride and an ether, e.g., boron trifluoride-ethyl ether complex
  • metal chlorides such as aluminum chloride and stannic chloride
  • acidic clays such as aluminum chloride and stannic chloride
  • the terpene-phenol adducts are in all cases not a simple chemical compound but rather a mixture of compounds, principally phenolic ethers and terpenylated phenol.
  • the adduct of 2 moles of camphene and 1 mole of p-cresol is a mixture of compounds in which mixture the principal ingredient is diisobornyl-pcres-ol (the isobornyl radical being formed by isomerization of camphene) but which also contains lesser amounts of the isobornyl ether of p-cresol.
  • hydroxyphenoxy substituted triazines which can be used to produce the compositions of the invention are also well known. Particuarly preferred are the hydroxyphenoxy tn'azines "described in Belgian 610,994. Inclusive of such compounds are the m-ono-, di-, or tri(hydroxyphenoxy)-l,3,5-triazines, and particularly 4,6-di(4-hy droxy-3,S-di-tert-butylphenoxy) 2-S-decyl-l,3,5-triazine, and the like.
  • the amount of the nickel salt and phenolic antioxidant incorporated in the polyolefin can be varied from a very small stabilizing amount up to several percent, but outstanding results have been obtained when from about 0.1 to about 5% of the nickel salt of the hydrocarbon carboxylic acid is used in combination with about 0.1 to about 5% of the phenolic antioxidant, based on the weight of polymer.
  • the nickel salt and the phenolic antioxidant used in accordance with this invention may be admixed with the polyolefin by any of the usual procedures for incorporating a stabilizer in a solid material.
  • a simple method is to dissolve the stabilizers in a low-boiling solvent such as of reactants and the catalyst employed. Consequently,
  • the adducts employed in the invention are incapable of structural definition.
  • thiobispheno-ls that can be used in accordance with the invention are well known materials and suitably include such compounds as benzene or hexane, and, after thoroughly mixing the solution with the polymer in flake or other such form, evaporating the solvent; or they may be incorporated by various means of mechanical mixing, etc.
  • the stabilizing combination of this invention may be used in combination with other stabilizers such as other ultra-violet light absorbers, antacids such as calcium soaps, organic phosphites or other antioxidants.
  • Other materials may also be incorporated in the polymer, as, for example, pigments, dyes, fillers, etc.
  • RSV as used herein denotes reduced specific viscosity, which is the specific viscosity divided by concentration of a 1.0% weight/ volume solution of polymer in decahydronaphthalene at C. All parts and percentages are by weight unless otherwise stated, and the percentage of stabilizer is based on the weight of polymer.
  • Examples [-17 of about 167 C. and a reduced specific viscosity of 4.0' With various amounts of the combination-of stabilizers described by the invention.
  • Each composition was' extruded into molding powder at 210 C. and the molding powder pressed into sheets 25 mils thick. Strips cut from each sheet, and 0.5 inch wide, were fastened onto pieces of white cardboard and exposed to outdoor weathering in Miami, Florida, at a 45 angle facing south. During the exposure, the development of brittleness in each strip was observed by periodically folding it to an angle of 180 and noting any change taking place at the fold line. The following rating schedule was used to evaluate the degree of brittleness: Y
  • each composition also contained 04 part calcium stearate as an antacid.
  • Example 18 Examples 19-20 The procedure of Example 3 was repeated using nickel 2,2,4,4-tetramethyl pentanoate and nickel 2,4,6-trimethyl of the nonylphenol-acetone reaction product of Examples 3-8, and 0.1 part calcium stearate as an extrusion aid with and without various of the nickel carboxylates of the invention, the amount of nickel carboxylate when used being equivalent to 0.12 part nickel per 100 parts of blend.
  • the yarns were clamped in a picture frame type holder and exposed to outdoor weathering in Miami, Florida, at a angle facing south.
  • Examples 21-26 In these examples 210-denier, 35-filament yarns (6 denier per filament) were prepared by melt spinning at 270 C. various blends of 100 parts of stereoregular polypropylene having a birefringent melting point of about tridecanoate (Example 28), the amount of nickel car-- 'boxylate being equivalent to 0.12 part nickel per 100 parts of the blend. Tenacity and elongation data for these compositions after outdoor exposure are tabulated 167 C. and a reduced specific viscosity of 3.6, 0.15 part below.
  • a polyolefin selected from the group consisting of polyethylene and a stereoregular polymer of a mono-w olefin having at least 3 carbon atoms containing as a light stabilizer therefor, based on the weight of the polyolefin, from about 0.1 to about 5% of a nickel salt of a hydrocarbon carboxylic acid containing 2 to 22 carbon atoms and from about 0.1 to about 5% of a phenolic antioxidant selected from the group consisting of trialkylphenols, aralkyl dialkyl substituted phenols, dialkylhydroxybenzyl substituted phenols, poly(alkylphenol) substituted hydrocarbons, hydroxyphenyl polyalkylchromans, adducts of an alkylphenol and a cyclic terpene, thiobis(alkylphenol)s, and hydroxyphenoxy substituted triazines.
  • nickel salt is selected from the group consisting of nickel 2-ethylhexanoate, nickel 2,2,4,4-tetrarnethylpentanoate, 2,4,6- trimethylheptanoate, nickel tridecanoate, nickel palmitate, nickel stearate, nickel caprylate, and nickel caprate.

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Description

United States Patent 3,310,510 POLYOLEFINS STABILIZED WITH THE COMBINA- TION OF A NICKEL SALT OF A CARBOXYLIC ACID AND A PHENOLIC ANTIOXHDANT David S. Breslow, Wilmington, DeL, assignor to Hercules Incorporated, a corporation of Delaware No Drawing. Filed July 30, 1964, Ser. No. 386,441 6 Claims. (Cl. 260-23) This application is a continuation-in-part of my copending application Serial No. 215,269, filed August 7, 1962, which is now abandoned.
The present invention relates to polyolefin compositions and, more particularly, to the stabilization of polyethylene and stereoregular polymers of propylene and higher ot-olefins against degradation by light.
Highly crystalline, high molecular weight stereoregular polymers of ethylene, propylene, and higher a-olefins are well known and widely used. However, one of the deficiencies of such polymers which must be overcome to enable their use in many applications is poor stability to light.
It is known from U.S. 2,984,634 that the dyeing properties of crystallizable polymers of olefins can be improved by incorporating in such polymers a small amount of a nickel salt of a carboxylic acid containing 6-12 carbon atoms. No ability of these nickel salts to stabilize polyolefins is recognized by the patentees and it is in fact doubtful if they possess any such ability on their own.
In accordance with the present invention, it has been found that the combination of a nickel salt of a hydrocarbon carboxylic acid and a small amount of a phenolic antioxidant is highly effective in stabilizing polyethylene and the stereoregular polymers of propylene and higher a-olefins against degradation by light. Thus, the invention relates to polyethylene and stereoregular polymers of and-olefin having at least 3 carbon atoms containing as light stabilizer therefor a small amount of a nickel salt of a hydrocarbon carboxylic acid containing 2 to 22 carbon atoms and a phenolic antioxidant. By the term hydrocarbon carboxylic acid is meant any carboxylic acid derived from a hydrocarbon by substituting a COOH group for a hydrogen atom.
Although any polymer of a Il'lOIlO-u-Olfififl having at least 2 carbon atoms can be stabilized by means of the invention, the invention is particularly useful is stabilizing stereoregular polymers of monoolefins having from 3 to 6 carbon atoms, including, for instance, polypropylene, poly (butene 1), poly(pentene 1), poly(3 methylbutene-l), and poly(4 methylpentene 1). Polyethylene, even though it degrades under the influence of light by a mechanism somewhat different than the above stereoregular polymers, is also susceptible to stabilization by the invention.
The nickel salts of the hydrocarbon carboxylic acids that are used to produce the compositions of the invention are known to the art and include, by way of example, the nickel salts of isobutyric, isovaleric, caproic, 2-ethylbutyric, 2-methyl-pentanoic, n-octanoic, 2-ethylhexanoic, 2,2,4,4-tetramethylpentanoic, 2,4,6-trimethylheptanoic, 5,7-dimethyloctanoic, pelargonic, lauric, tridecanoic, myristic, palmitic, stearic, naphthenic, 3-methylcyclohexane, carboxylic, 4-isopropylcyclohexane carboxylic, cyclohexane acetic, bicyclo(2,2,1) carboxylic, p(1,1,
being 2,6-di-tert-butyl-p-cresol.
3,310,510 Patented Mar. 21, 1967 3,3-tetramethylbutyl) benzoic, 2,4-diisopropyl naphthoic, octyl succinic, 2-decyl glutaric, 2,5-dibutyl adipic, sebacic acids, and the like. Mixtures of acids such as, for example, coconut fatty acids, are also suitable.
The phenolic antioxidants used to produce the compositions of the invention are also well known. Such antioxidants include, for example, polysubstituted phenols, poly(alkylphenol) substituted hydrocarbons, hydroxyphenyl polyalkylchromans, adducts of an alkylphenol and a cyclic terpene, thiobis(alkylphenol)s, and hydroxyphenoXy substituted triazines. The A-stage para-tertiary alkylphenol-formaldehyde resins such as are described in US. 2,968,641 are also suitable.
The polysubstituted phenols that can be used are either dior trisubstituted phenols. Particularly preferred are the 2,4,6-trialkylphenols described in US 2,581,907 to Smith, Jr., et al., the 2-aralkyl-4,6-dialkyl substituted phenols described in US. 2,967,853 to Spacht, and the mono-, di-, and tri(dialkyl hydroxybenzyl) phenols described in US. 3,053,803 to latte, Rocklin, and Van Winkle. Inclusive of the trialkylphenols are: 2,4-dimethyl 6 tert-butylphenol, 2,4-dirnethyl-6-(alpha,alpha,gamma,gamma tetramethylbutyl) phenol, 2,6-di-tert-butyl-4- methylphenol, 2-methyl-4,6 di tert-butylphenol, 2,6-ditert-butyl-4-sec-butylphenol, 2,4,6-tri-tert-butylphenol, 2, 4,6-triethylphenol, 2,4,6-tri-n-propylphenol, 2,4,6-triisopropylphenol, 2,6-di-tert-octyl-4-propylphenol, 2,6-di-tertbutyl-4-ethylphenol, 2,4-dicyclohexyl-6-methylphenyl,- 2- isopropyl 4 methyl 6-tert-butylphenol, 2,4-dimethyl- 6- tert-amylphenol, 2,4-di-tert-amyl--methylphenol, 2,6-di tert butyl 4-isopropylphenol, 2,6,di-tert-amyl-4-methy1- phenol, 2,6-di-tert-amyl-4-isopropylphenol, 2,4-diisopropyl-6-tert-butylphen0l, 2,4-diisopropyl-6-sec-hexylphenol, 2 alphaphenylethyl-4-methyl-6-tert-butylphenol, and 2 alphaphenylethyl-4-methyl-o-tert-octylphenol. The preferred compounds of this class are those which"have primary or secondary aralkyl groups or secondary or tertiary alkyl groups at the 2- and 6-position and a normal alkyl group at the 4-position, a representative of this class More preferably, the normal alkyl group in the 4-position is one containing from about 1 to 20 carbon atoms while the secondary or tertiary alkyl groups in the 2- and 6-positions each contain from about 3 to 20 carbon atoms.
The preferred aralkyl dialkyl substituted phenols are those which have a primary aralkyl radical, a secondary aralkyl radical, or a tertiary alkyl radical having 4 to 12 carbons ortho to a hydroxyl group. Particularly suitable are 2-alphaphenylethyl-4-methyl-6-tert-butylphenol and 2- alphaphenylethyl-4-methyl-6-tert-octylphenol. Particularly preferred mono-, di-, and tri(dialkyl hydroxylbenzyl) phenols include: p-(3,5-di-tert-butyl-4-hydroxybenzyl) phenol, p-(3,Sadiisopropyl-4-hydroxybenzyl)phenol, o-(3- methyl-S-isopropyl-4-hydroxybenzyl)phenol, o (3-butyl- 5-tert-amyl-4-hydroxybenzyl)phenol, o-(3-5-di-tert-arnyl 4 hydroxybenzyl)phenol, 2,6 di(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, 2,6 di(3,5 di tert butyl 4 hydroxybenzyl)-4-methylphenol 2,6 di(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 2,6 di(3-rnethyl-5- tert-amyl-4-hydroxybenzyl)phenol, 2,6-di(3,5-diisopropyl 3 4 hydroxybenzyl) phenol, 2,6-di(3,5 di-tert-hexyl-4-hydroxybenzyl)phenol, 2,4 di(3,5-diisopropyl 4-hydroxybenzyl)-6-tert-butylphenol, 2,4 di(3,5-di-tert-amyl-4-hydroxybenzyl)phenol, 2,4-di(3-isopropyl-5-tert-buty1-4-hydroxybenzyl)phenol, 2,4 di(3,S-di-tert-butyl-4-hydroxybenzyl)phenol, 2,4,6 tri(3,5-di-tert-butyl-4-hydroxybenzyl)phenol, 2,4,6 tri(3 methyl--tert-butyl-4-hydroxybenzyl)phenol, 2,4,6 tri(3,5-diisopropyl-4-hydroxybenzyl)phenol, and 2,4,6-tri(3-isopropyl-5-tert-octyl 4 hydroxybenzyl -3 -methylphenol.
The second class of phenolic antioxidants, the poly- (alkylphenol) substituted hydrocarbons, that can be used are either bis, tris, or tetrakis phenols and preferably are al'kylidene-bis (alkylphenol)s, a,w-bisal-kylidene-bis (alkylphenol)s, cycloalkylidene-bis(alkylphenol)s, benzylidenebis(=alky1phenol)s, and bis or tris(dialkyl hydroxybenzyl) alkyl benzenes. The alkylidene-bis(alkylphenol)s are characterized by the general formula wherein R is an alkylidene radical of l to 5 carbon atoms and wherein R is an alkyl group of 1 to 12 carbon atoms and n is an integer from 1 to 3 and m is an integer from 1 to 2. When more than one R substituent is present on a phenyl group, each R can be the same or dilferent. Exemplary of the alkylidene-bis(alkylphenol)s that may be used are 2,2'-methylene-bis 5--isopropylphenol 2,2'-methylene-bis (4-methyl-6-isopropylphenol 2,2'-methylene-bis(4-methy1-6-tert-butylpheno1) 2,2'-methylene-bis 4-tert-butyl-6-methylphenol 2,2' methylene-bis-(4,6-di-tert-butylphenol 2,2-methylene-bis 4-nonylphenol 2,2'-methylene-bis [4methyl-6-( l-methylcyclohexyl) phenol] 2,2'-methylene-bis (4-decyl-phenol) 4,4'-methylene-bis( 5-methyl-2-tert-butylphenol 4,4'-methylene-bis 5-methyl-2-( l-methylcyclohexyl) phenol] 4,4'-methylene-bis 2,6-di-tert-butylphenol 2,2'-isopropylidene-bis S-methylphenol) 4,4'-methylene-bis(2-methyl-6-tert-butylphenol), 2,2-ethylidene-bis 4-methyl- 6-tert-butylphenol) 2,2-ethylidene-bis 4,6-di-tert-buty1phenol) 2,2'-ethylidene-bis(4-octylphenol 2,2-ethylidene-bis(4-nonylphenol) 2,2'-isopropylidene-bis (4-methy1-6-isopropylphenol) 2,2'-isopropylidene-bis 4-i sopropylphenol) 2,2'-isopropylidene-bis 4-isopropyl-6-methylphenol 2,2-isopropylidene-bis (4-methyl=6-teIt-butylphenol) 2,2'-isopropylidene-bis 4-octylphenol) 2,2-isopropylidene-bis( 4-nonylphenol) 2,2-isopropylidene-bis (4-decylphenol) 2,2-n-butylidene-bis (4-methyl-6-tert-b utylphen ol 2,2'-isobutylidene-bis 4-methyl-6-tert-butylphenol) 2,2'-isobutylidene-bis(4-nonylphenol) 4,4-n-butylidene-bis (2-tert-butyl-S-methylphenol and the corresponding a,w-bis alkylidene -bi's alkylphenol s.
Also suitable are the cycloalkylidene bis(alkylphenol)s, the benzylidene-bis (alkylphenol)s, and the his or tris (dialkyl hydroxybenzyl)alkyl benzenes. these phenols are Exemplary of The hydroxyphenyl polyalkylchromans are the 2- (or 4) (*2-hydroxyphenylchromans which have one of the following general formulae:
where each R may be hydrogen or alkyl, but at least one R in each of the aromatic rings is alkyl. These compounds may also be named as benzopyrans. Thus, the 2(2-hydroxyphenyl)chromans may be named as 2,3-dihydro-2(2'-hydroxyphenyl)-1,4-benzopyrans or 3,4-dihydro-2(2-hydroxyphenyl)-1,2-benzopyrans and the 4(2'- hydroxyphenyl)chromans may be named as 2,3-di-hydro- 4(2-hydroxyphenyl) 1,4 benzopyrans or 3,4-dihydro- 4(2'-hydroxyphenyl)-1,2-benzopyrans. The 2(2'-hydroxyphenyl)chromans are also sometimes named as flavans, i.e., 2'-hydroxy-flavans. The alkyl substituents in each of the aromatic rings may be any alkyl radical, as, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertbutyl, amyl, hexyl, isohexyl, octyl, isooctyl, 'Z-ethylhexyl, nonyl, isononyl, decyl, undecyl, dodecyl, etc. Preferably, at least one alkyl radical in each aromatic ring will contain at least four carbon atoms or the sum of the carbon atoms in the alkyl radicals in each ring will be at least four. Exemplary of these 2- (or 4) (2-hydroxyphenyl)chromans are 2 2-hydroxyphenyl -2,4,4,5 ',6-pentamethylchroman,
4 2-hydroxyphenyl -2,2,4,5 ,6-pentamethylchroman,
2 2-hydroxyphenyl) -5 ,6-diisopropyl-2,4,4-
trimethylchroman,
2 (2-hydroxyphenyl) -5 '-6-diisopropyl-2,4,4,3 ,8-
pent amethylchrom an,
2 2-hydroxyphenyl -5 ,6-di-tert-butyl-2,4,4-
trimethylchroman,
4 2-hydroxyphenyl -5 ',=6-di-tert-buty1-2,2,4-
trimethylchrom an,
2)( 2'-hydroxyphenyl) -5 ,6-dioctyl+2,4,4-trimethylchroman,
2 (2'-hydroxyphenyl -S ',6-dinonyl-2,4,4-trimethylchroman,
4 2-hydroxyphenyl) -5 ,6-dinonyl-2,2,4-trimethylchroman,
described frequently in the prior art.
5 2 (2-hydroxyphenyl) -5',6-didecyl-2,4,4-trimethylchroman, etc.
The terpene-phenol adducts that are used in accordance with the invention are known materials that have been Generically defined, they are adducts of phenol or an alkylphenol that contains from 1 to 2 alkyl substituents of 1 to 10 carbon atoms each and a cyclic unsaturatedterpene or dihydroterpene of empirical formula C H or C H respectively. They'can be prepared by condensing phenol, or an alkylphenol, with the terpene, or dihydroterpene, in varying ratios in the presence of an acidic catalyst.
Suitable cyclic terpenes and dihydroterpenes from which the aforesaid adducts can be made include carvomenthene, dipentene, a-pinene, a-terpinene, terpinolene, Z-menthene, 3-menthene, dihydroterpinolene, dihydrodipentene, camphene, A -carene, p-pinene, and the like. Suitable phenols, in addition to phenol itself, include the various isomeric cresols, 2,4-xylenol and other isomeric xylenols, p-sec-butylphenol, p-isopropylphenol, o-isopropylphenol, m isopropylphenol, 0,0 diisopropylphenol, o,o'-di-tert-butylphenol, o amylphenol, o nonylphenol, and similar compounds.
The two reactants can be condensed in varying ratios. Any ratio within the range of 0.3 to 3 moles of terpene or dihydroterpene per mole of the phenolic compound is satisfactory, but it is preferred to employ a ratio within the narrower range of 0.5 to 2.5 moles of terpene or dihydroterpene per mole of the phenolic compound.
The adduct formation is carried out by contacting the two reactants in the presence of an acid catalyst at a temperature within the range of about to 150 C. and allowingthe reaction to proceed. An inert solvent may be used as a reaction medium for convenience, if so desired. Normally, the reaction will go to substantial completion in from 1 /2 to 5 /2 hours. Upon termination of the reaction, unconsumed reactants and volatile byproducts can be removed by distillation at reduced pres sure since the adducts themselves are high boiling materials.
The acid catalyst can be any of those acids or acidic compounds that are useful catalysts in condensation reactions generally. These include mineral acids such as sulfuric acid, organic acids such as p-toluene sulfonic acid, boron trifluoride and its derivatives, as, for instance, complexes of boron trifluoride and an ether, e.g., boron trifluoride-ethyl ether complex, metal chlorides such as aluminum chloride and stannic chloride, and acidic clays.
The terpene-phenol adducts are in all cases not a simple chemical compound but rather a mixture of compounds, principally phenolic ethers and terpenylated phenol. Thus, for instance, the adduct of 2 moles of camphene and 1 mole of p-cresol is a mixture of compounds in which mixture the principal ingredient is diisobornyl-pcres-ol (the isobornyl radical being formed by isomerization of camphene) but which also contains lesser amounts of the isobornyl ether of p-cresol.
In the case of other terpenes, or dihydroterpenes, and other phenols, similar adducts are formed in which the proportion of ingredients will vary depending on the ratio and the like.
The hydroxyphenoxy substituted triazines which can be used to produce the compositions of the invention are also well known. Particuarly preferred are the hydroxyphenoxy tn'azines "described in Belgian 610,994. Inclusive of such compounds are the m-ono-, di-, or tri(hydroxyphenoxy)-l,3,5-triazines, and particularly 4,6-di(4-hy droxy-3,S-di-tert-butylphenoxy) 2-S-decyl-l,3,5-triazine, and the like.
The amount of the nickel salt and phenolic antioxidant incorporated in the polyolefin can be varied from a very small stabilizing amount up to several percent, but outstanding results have been obtained when from about 0.1 to about 5% of the nickel salt of the hydrocarbon carboxylic acid is used in combination with about 0.1 to about 5% of the phenolic antioxidant, based on the weight of polymer.
The nickel salt and the phenolic antioxidant used in accordance with this invention may be admixed with the polyolefin by any of the usual procedures for incorporating a stabilizer in a solid material. A simple method is to dissolve the stabilizers in a low-boiling solvent such as of reactants and the catalyst employed. Consequently,
the adducts employed in the invention are incapable of structural definition.
The thiobispheno-ls that can be used in accordance with the invention are well known materials and suitably include such compounds as benzene or hexane, and, after thoroughly mixing the solution with the polymer in flake or other such form, evaporating the solvent; or they may be incorporated by various means of mechanical mixing, etc.
The stabilizing combination of this invention may be used in combination with other stabilizers such as other ultra-violet light absorbers, antacids such as calcium soaps, organic phosphites or other antioxidants. Other materials may also be incorporated in the polymer, as, for example, pigments, dyes, fillers, etc.
The following examples will illustrate the degree of stabilization that is obtained when a polyolefin is stabilized in accordance with this invention. The term RSV as used herein denotes reduced specific viscosity, which is the specific viscosity divided by concentration of a 1.0% weight/ volume solution of polymer in decahydronaphthalene at C. All parts and percentages are by weight unless otherwise stated, and the percentage of stabilizer is based on the weight of polymer.
Examples [-17 of about 167 C. and a reduced specific viscosity of 4.0' With various amounts of the combination-of stabilizers described by the invention. Each composition was' extruded into molding powder at 210 C. and the molding powder pressed into sheets 25 mils thick. Strips cut from each sheet, and 0.5 inch wide, were fastened onto pieces of white cardboard and exposed to outdoor weathering in Miami, Florida, at a 45 angle facing south. During the exposure, the development of brittleness in each strip was observed by periodically folding it to an angle of 180 and noting any change taking place at the fold line. The following rating schedule was used to evaluate the degree of brittleness: Y
1=Unchanged from original condition 2=Slight surface crazing on fold 3==Sh-allow cracks on fold 4=Breaks in cheesy manner, but pieces hang together; considered failure 5=Brittle break failure Table-I shows the formulation of each composition and the results of outdoor exposure.
TABLE I Compositions 1 N onylphenol-acetonc reaction product 0.5 1.0 1.5 2.0 0.5 1.0 Mixture of 4,4-n-butylidene bis(2- tert-butyl-5-methylphenol) and diphenyl isooctyl phosphite 5 1. 7 1. 7 2. 2 4,4-n-butylidene bis(2-tert-loutyl-5- methylphenol) 1.1 1.1 1. 6 2, 2-methylene bis(4-methyl-6-tertbutylphenol) 1. 0 1. 0 1. 5 Nickel 2-ethyl hexanoate 0. 5 1. O 0. 5 0. 5 0. 5 1. 0 0. 5 0. 5 0. 5
Ratings after Florida Exposure 30,000 Langleys--- 3 3 2 3 5 5 5 4 5 5 5 5 5 5 5 20,000 Langleys- 2 3 2 2 5 5 2 3 3 5 5 5 5 5 5 1 In parts per 100 parts polymer, each composition also contained 04 part calcium stearate as an antacid.
2 Prepared by reaction of 2 moles n-nonylphenol and 1 mole of acetone under acid conditions [mixture of 2,2-isopropy1idene-bis(4-nonylphenol) 8 Mixture prepared by heating 1 part of the phenol per 2.5 parts of the phosphite at elevated temperature according to the procedure described in Belgian 604,245 to improve compatibility with the polymer.
4 Brittle on molding; could not be tested.
Example 18 Examples 19-20 The procedure of Example 3 was repeated using nickel 2,2,4,4-tetramethyl pentanoate and nickel 2,4,6-trimethyl of the nonylphenol-acetone reaction product of Examples 3-8, and 0.1 part calcium stearate as an extrusion aid with and without various of the nickel carboxylates of the invention, the amount of nickel carboxylate when used being equivalent to 0.12 part nickel per 100 parts of blend. The yarns were clamped in a picture frame type holder and exposed to outdoor weathering in Miami, Florida, at a angle facing south. Embrittlement due to exposure Was evaluated at intervals by removing some of the samples and measuring the percent elongation and the force (grams/ denier) at break when a 4" strand of the yarn was extended at the rate of 4"/min. in a constant rate of specimen extension machine at 23 C. Table II gives details of the compositions and the results of tenacity and elongation tests before and after outdoor exposure.
TABLE 11 Florida Exposure (Langleys) Ex. No. Nickcl Carboxylate 0 30,000 40,000 50,000 60,000
Tenacity Elong. Tenacity Elong. Tenacity Elong. Tenacity Elong. Tenacity Elong.
(g./d.) (Percent) (g./d.) (Percent) (g./d.) (Percent) (g./d.) (Percent) (g./d.) (Percent) 5. 8 44 3. 7 15 3. 2 21 1. 6 6 0. 64 2 5. 7 48 5. 4 34 5. 3 43 4. 9 32 2. 7 20 5. 6 43 4. 7 26 3. 6 22 2. 8 14 1. 9 10 5. 5 47 5. 0 32 4. 2 30 3. 7 19 2. 8 14 Nickel caprylate 5. 5 66 4. 2 23 2. 7 16 2. 2 9 l. 0 7 Nickel caprate 5. 5 3. 5 26 2. 8 16 2. 0 l0 1. 2 5
heptanoate in place of nickel 2-ethyl hexanoate. Each Examples 26-28 of the compositions gave an outdoor exposure rating in Florida of 2 at 20,000 Langleys and 3-4 at 30,000 Langleys.
Examples 21-26 In these examples 210-denier, 35-filament yarns (6 denier per filament) were prepared by melt spinning at 270 C. various blends of 100 parts of stereoregular polypropylene having a birefringent melting point of about tridecanoate (Example 28), the amount of nickel car-- 'boxylate being equivalent to 0.12 part nickel per 100 parts of the blend. Tenacity and elongation data for these compositions after outdoor exposure are tabulated 167 C. and a reduced specific viscosity of 3.6, 0.15 part below.
TABLE III Outdoor Exposure (Langleys) EX. N0. 30,000 40,000 50,000 60,000 78,000
Tenacity Elong. Tanacity long. Tenacity Elong. Tenacity Elong. Tenacity Elong. Tenacity Elong. (g./d (percent) (g./d (percent) (g. Id.) (percent) (g./d (percent) (g. /d.) (percent) (g./d.) (percent What I claim and desire to protect by Letters Patent is:
1. A polyolefin selected from the group consisting of polyethylene and a stereoregular polymer of a mono-w olefin having at least 3 carbon atoms containing as a light stabilizer therefor, based on the weight of the polyolefin, from about 0.1 to about 5% of a nickel salt of a hydrocarbon carboxylic acid containing 2 to 22 carbon atoms and from about 0.1 to about 5% of a phenolic antioxidant selected from the group consisting of trialkylphenols, aralkyl dialkyl substituted phenols, dialkylhydroxybenzyl substituted phenols, poly(alkylphenol) substituted hydrocarbons, hydroxyphenyl polyalkylchromans, adducts of an alkylphenol and a cyclic terpene, thiobis(alkylphenol)s, and hydroxyphenoxy substituted triazines.
2. The composition of claim 1 in which the polymer is polypropylene.
3. The composition of claim 1 in which the polymer is polyethylene.
4. The composition of claim 1 in which the nickel salt is selected from the group consisting of nickel 2-ethylhexanoate, nickel 2,2,4,4-tetrarnethylpentanoate, 2,4,6- trimethylheptanoate, nickel tridecanoate, nickel palmitate, nickel stearate, nickel caprylate, and nickel caprate.
5. Stereoregular polypropylene containing as a light stabilizer therefor, based on the Weight of the polypropylene, from about 0.1 to about 5% of nickel Z-ethylhexano- References Cited by the Examiner UNITED STATES PATENTS 2,984,634 5/1961 Caldwell et a1. 26023 3,006,885 10/1961 Dickson 26045.75 3,006,886 10/1961 Schilling 26045.'75 3,072,601 1/1963 'Breslow 2'60--45.75 3,074,909 1/ 1963 Matlack 2'6045.75 3,074,910 1/1963 Dickson 260-45.75 3,102,107 8/1963 Soeder 26045.75 3,107,232 10/1963 Matlack 260- 1575 3,127,372 3/1964 Matlack 26045.75
LEON J. BERCOVITZ, Primary Examiner. DONALD E. CZAJA, Examiner.
R. W. RAUCHFUSS, Assistant Examiner.

Claims (1)

1. A POLYOLEFIN SELECTED FROM THE GROUP CONSISTING OF POLYETHYLENE AND A STEREOREGULAR POLYMER OF A MONO-AOLEFIN HAVING AT LEAST 3 CARBON ATOMS CONTAINING AS A LIGHT STABILIZER THEREFOR, BASED ON THE WEIGHT OF THE POLYOLEFIN, FROM ABOUT 0.1 TO ABOUT 5% OF A NICKEL SALT OF A HYDROCARBON CARBOXYLIC ACID CONTAINING 2 TO 22 CARBON ATOMS AND FROM ABOUT 0.1 TO ABOUT 5% OF A PHENOLIC ANTIOXIDANT SELECTED FROM THE GROUP CONSISTING OF TRIALKYLPHENOLS, ARALKYL DIALKYL SUBSTITUTED PHENOLS, DIALKYLHYDROXYBENZYL SUBSTITUTED PHENOLS, POLY(ALKYLPHENOL) SUBSTITUTED HYDROCARBONS, HYDROXYPHENYL POLYALKYLCHROMANS, ADDUCTS OF AN ALKYLPHENOL AND A CYCLIC TERPENE, THIOBIS(ALKYLPHENOL)S, AND HYDROXYPHENOXY SUBSTITUTED TRIAZINES.
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US3359234A (en) * 1963-06-26 1967-12-19 American Cyanamid Co Stabilized polyolefins containing a nickel alkanoate and a thio-bisphenol
US3464943A (en) * 1967-09-28 1969-09-02 Eastman Kodak Co Stabilizing polyolefins with certainnickel and hydroxybenzotriazole compounds
US3544512A (en) * 1968-01-22 1970-12-01 Dow Chemical Co Stabilized polyolefin compositions
US4052351A (en) * 1975-08-04 1977-10-04 Phillips Petroleum Company Stabilization of olefin polymers
US5096955A (en) * 1991-01-14 1992-03-17 The Dow Chemical Company Stabilized polyethylene resins and method of stabilization

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